Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
  • B32B9/02—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
  • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B9/041—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/0895—Manufacture of polymers by continuous processes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
  • C08G18/6484—Polysaccharides and derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
  • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
  • C09J103/02—Starch; Degradation products thereof, e.g. dextrin
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
  • C09J123/10—Homopolymers or copolymers of propene
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
  • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2400/00—Presence of inorganic and organic materials
  • C09J2400/10—Presence of inorganic materials
  • C09J2400/16—Metal
  • C09J2400/163—Metal in the substrate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2400/00—Presence of inorganic and organic materials
  • C09J2400/20—Presence of organic materials
  • C09J2400/22—Presence of unspecified polymer
  • C09J2400/226—Presence of unspecified polymer in the substrate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2403/00—Presence of starch
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2423/00—Presence of polyolefin
  • C09J2423/10—Presence of homo or copolymers of propene
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2451/00—Presence of graft polymer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
  • Y10T428/2852—Adhesive compositions
  • Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
  • Y10T428/2883—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer of diene monomer [e.g., SBR, SIS, etc.]

Definitions

• the present invention relates to a method of manufacturing an article comprising a multilayer structure including at least one layer of a composition based on starchy material and polypropylene. Another object of the invention is the article obtained by this method.
• the invention also relates to the use of said composition as a binder used in the fields of the transformation and implementation of plastics such as extrusion, co-extrusion, injection, co-injection or the overmolding.
• multilayer structures In many fields of industry, it is necessary to use multilayer structures in products such as films, tubes or bottles. It is possible to combine layers of different materials: the multilayer structures may require the combination of different functionalities and each of the layers of the structure provides a particular function to the final structure.
• the industrial processes for manufacturing these products comprising these multilayers generally consist in the application of a polymer in the molten state to another layer comprising an organic polymer or a metal.
• co-injected or overmoulded products comprising a layer having a soft feel of a particular ethylene-co-propylene copolymer (EPR) on a more rigid polyethylene high density (HDPE) polymer body are manufactured.
• EPR layer naturally adhering to HDPE because of their relatively similar chemical natures and polarities.
• plastic bottles for containing fruit juice by combining a layer of ethylene-co-vinyl alcohol copolymer (EVOH) between two layers of low density polyethylene (LDPE): the LDPE layers give the structure water barrier properties and the intermediate layer of EVOH provides gas barrier properties.
• LDPE low density polyethylene
• Other examples of multilayer structures can be cited such as "bricks" for the food industry combining an aluminum layer with a layer of cardboard, or tubes for transporting hot water combining a polyamide layer ( PA) to a layer of polypropylene (PP).
• PA polyamide layer
• PP polypropylene
• the materials of these layers may be of a chemical nature and of a substantially similar or different polarity.
• the multilayer structures may also comprise several layers of a material of a chemical nature and of a substantially similar polarity, for example several layers of the same material: by way of example, since the EVOH is a polymer that is not very flexible and is sufficiently "brittle" ", We can associate different thin layers of EVOH in a structure: this allows to obtain a more flexible structure in comparison with a structure comprising a single layer of EVOH of thickness equal to the sum of the thicknesses of the thin layers.
• An adhesive layer, or tie layer, is therefore used to associate these layers, this binder having to adhere to the materials of the two different layers to be associated with each other.
• ⁇ find a suitable "binder" to bond the different layers to be associated in the structure.
• thermoplastic polymer layers constituting the article are contacted in the molten or softened state.
• These techniques are difficult to implement because it is necessary that the adhesive layer in the molten or softened state has particular properties: besides the fact that the composition must be able to adhere to the different layers of the structure on which it is placed. in contact, this composition must also have a fluidity and a dimensional stability in the molten state. to be used in these coextrusion processes. This is necessary so that the layer of adhesive composition of the structure can retain its dimensions during the cooling of the article.
• compositions based on starchy material and polypropylene have an ability, when it is in the molten or softened state, to adhere to a multitude of supports, and this in a sufficiently fast to be used in continuous industrial processes.
• the composition is placed in hot contact on another layer of a support, said support layer being solid or itself in the molten or softened state during this bringing into contact.
• These supports may be based on metal or polymer, thermoplastic or thermoset, both polar and nonpolar. This particular composition is therefore of particular interest for the manufacture of multilayer structures.
• this composition may be used in a method of manufacturing an article comprising a multilayer structure, wherein said structure is manufactured by adhering different layers, and whose adhesive composition layer is in the molten or softened state upon contacting with the other layers.
• the invention thus relates to a method of manufacturing an article comprising a multilayer structure containing:
• ⁇ and a second layer of an adhesive composition comprising by weight: a) from 15 to 40% of at least one starchy material;
• grafted polypropylene grafted monomer selected from unsaturated carboxylic acid anhydrides, unsaturated carboxylic acids, oxiranes, and silanes;
• the structure according to the invention may also further comprise a third layer based on metal or organic polymer, the second layer, located between the first and third layers, also adhering to said third layer.
• WO 2009/022195 describes a composition comprising a starchy material, a plasticizer, a polypropylene and a compatibilizer, which may be polypropylene grafted with maleic anhydride.
• the composition can be used for the manufacture of a monolayer film. It is possible to apply the film to an article made of paper, plastic, wood or composite material. However, this film is not applied hot on the article. The document therefore does not teach the manufacture of multilayer structures by a step of contacting in the molten or softened state of the composition described therein.
• the Applicant explains in part the ability of the adhesive composition according to the invention to adhere to substrates as diverse as PP, PE, PA, EVOH, paper or paper. aluminum by the choice of its constituents, in particular proportions, each of these constituents having a polar or apolar nature.
• the adhesive composition included in the structure according to the invention also has the advantage of being less expensive in comparison with the adhesives usually used in the field.
• the composition is printable, labable and has a soft feel. It can also be colored in the mass by the addition of pigments or dyes.
• the adhesive composition can therefore be used both in the outer layer and in the intermediate layer, that is to say between two other layers. Another advantage of this adhesive composition is that it meets the demand for "bio-sourced” origin product since it comprises starchy material extracted from plants.
• the adhesive composition preferably comprises 20 to 40% of starchy material, 20 to 30% of plasticizer of this starchy material, 10 to 30% of non-grafted polypropylene and preferably 10 to 30% of grafted polypropylene grafted monomer.
• the grafting monomer may be selected from maleic anhydride, maleic acid, acrylic acid, methacrylic acid, glycidyl methacrylate or glycidyl acrylate.
• the grafting monomer is an unsaturated carboxylic acid anhydride, most preferably maleic anhydride.
• the adhesive composition of the second layer may consist of at least 50% by weight of constituents a, b, c and d, advantageously at least 80%, preferably at least 90%.
• the adhesive composition of the second layer contains a binding agent comprising at least two functions that are reactive with respect to the starchy material, the plasticizer or the grafting monomer.
• the composition has a capacity of adhesion to the layers with which it is in contact even more important.
• the binding agent may advantageously be chosen from polyisocyanates, preferably from diisocyanates, most preferably from 4,4'-dicyclohexylmethane diisocyanate (H12MDI), methylenediphenyl diisocyanate (MDI) and toluene diisocyanate (TDI). , naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HMDI) and lysine diisocyanate (LDI).
• polyisocyanates preferably from diisocyanates, most preferably from 4,4'-dicyclohexylmethane diisocyanate (H12MDI), methylenediphenyl diisocyanate (MDI) and toluene diisocyanate (TDI).
• H12MDI 4,4'-dicyclohexylmethane diisocyanate
• MDI methylenediphenyl diisocyanate
• TDI tol
• the binding agent is advantageously present in the adhesive composition in an amount ranging from 0.1 to 15 percent resin (pcr), advantageously from 0.2 to 12 phr, preferably from 0.5 to 5 phr, the sum of the components a, b, c and d being equal to 100 pcr.
• At least some or all of the functions of the binding agent may have reacted with the plasticizer, the starchy material and / or the graft-grafted monomer on the polypropylene.
• reaction of the binding agent with the plasticizer, the starchy material and / or the graft-grafting monomer can be carried out on the polypropylene by reactive extrusion.
• the adhesive composition advantageously has a melt flow index (MFI) in the range from 0.1 to 200 g / 10 min (ISO 1133, 190 ° C, 2, 16 kg), for example from 0.2 to 90 g / 10 min, preferably from 0.25 to 50 g / 10 min, most preferably from 0.3 to 10 g / 10 min.
• MFI melt flow index
• the choice of this preferred composition is determined, as will be seen below, by the choice and the proportions of each of its constituents, which makes it possible to obtain an adhesive composition that is even more efficient in the field of coextrusion.
• the plasticizer of the amylaceous material is chosen from glycerol, isosorbide, sorbitans, sorbitol, mannitol, polyethylene glycol, polypropylene glycol or a mixture thereof, the plasticizer preferably comprising at least 50% by weight glycerol.
• the water content of the adhesive composition relative to its total mass is less than 10% by weight, preferably less than 5%, preferably less than 2%. It may be greater than 0.05% or even 0.2%.
• This water content can be determined by the Karl Fischer method which is the principle: the Fischer reagent is a methanolic solution of iodine, sulfur dioxide and an amine other than pyridine. In the absence of water the reagent is stable, but in the presence of water the sulfur dioxide is oxidized by the iodine following the reaction:
• the organic polymer of the first or third layer may be chosen from homopolymers and copolymers of ethylene (PE), homopolymers or copolymers of propylene (PP), homopolyamides and copolyamides (PA), poly (alcohol) vinyl) (PVOH), homopolymers and copolymers of styrene (PS), acrylic homopolymers or copolymers, polyesters, chlorinated polymers and fluoropolymers, polyacetals, polyimides, polysulfones, polycarbonates (PC), polacrylonitriles, polyurethanes (PU), phenylene polysulfides (PPS), thermoplastic starches (TPS) or a mixture thereof.
• PE ethylene
• PP propylene
• PA homopolyamides and copolyamides
• PVOH poly (alcohol) vinyl)
• PS polymers and copolymers of styrene
• acrylic homopolymers or copolymers polyesters,
• the organic polymer can be:
• ⁇ a polyethylene selected from high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-vinyl co-vinyl acetate copolymer (EVA), ethylene-co-acrylate alkyl, ethylene-co-alkyl methacrylate copolymers, ethylene-co-acrylic acid copolymer, ethylene-co-methacrylic acid copolymer, ethylene-co-vinyl alcohol copolymer (EVOH); ⁇ the poly (vinyl alcohol) (PVOH);
• PP polypropylene chosen from isotactic polypropylene (iPP) or atactic polypropylene (APP); or
• PA6 polyamide 6
• PA6.6 polyamide 6.6
• PA1 1 polyamide 1 1
• PA12 polyamide 12
• the organic polymer may also be cellulose.
• the metal that can form the first or the third layer is preferably aluminum.
• the first or third layer is based on polyethylene, polypropylene, polyamide, polyester, cellulose or aluminum.
• the total number of layers of the structure according to the invention is preferably from 2 to 15 layers, for example from 3 to 1 1 layers.
• Preferred structures of the invention comprise at least one of the following layer combinations:
• the Applicant has found that the adhesive composition adhered particularly well to homopolymers and copolymers of ethylene, in particular those chosen from HDPE, LDPE and LLDPE.
• the invention also relates to an article comprising the multilayer structure.
• This article can be a film, a sheet, a tray, a bottle, a bottle, a tank, a pocket, a tube, a pipe, a bucket, a box, a dashboard, a tool handle, a handle door or carpet.
• the step of contacting the manufacturing method of this article may be carried out by an extrusion, coextrusion, co-injection, overmolding, coating, extrusion coating or extrusion rolling step. preferably by a coextrusion step.
• a particular object of the invention is a film manufacturing process carried out by a film coextrusion step, for example by coextrusion of jacket blowing, said film being a three-layer film of PE structure / adhesive composition / PE, preferably of LDPE structure / adhesive composition / LDPE.
• Another object of the invention is a method of manufacturing a hollow body, for example a bottle, a bottle or a tank, made by a coextrusion step of hollow body, said hollow body being of bilayer structure PE / adhesive composition, preferably HDPE structure / adhesive composition.
• the invention also relates to an article obtained from one of the methods described above.
• Another subject of the invention is the use of the adhesive composition as described above in an extrusion, co-extrusion, injection, co-injection or over-molding process for adhering a material. based on metal or organic polymer.
• the adhesive composition useful to the invention comprises
• grafted polypropylene grafted monomer chosen from unsaturated carboxylic acid anhydrides, unsaturated carboxylic acids, oxiranes and silanes.
• the starchy material used in the adhesive composition is preferably selected from granular starches, water-soluble starches and organomodified starches.
• a granular starch is in a state of semi-crystalline granules characteristic of the state in which it is naturally present in the reserve organs and tissues of higher plants, in particular in cereal seeds, leguminous seeds, apple tubers of land or cassava, roots, bulbs, stems and fruits.
• This natural semi-crystalline state is essentially due to the macromolecules of amylopectin, one of the two main constituents of starch.
• the starch grains In the native state, the starch grains generally have a degree of crystallinity which varies from 15 to 45%, and which essentially depends on the botanical origin of the starch and the possible treatment it has undergone.
• a granular starch can be of any botanical origin. It may be starch native to cereals such as wheat, maize, barley, triticale, sorghum or rice, tubers such as potato or cassava, or legumes such as peas and soya, starches rich in amylose or conversely, rich in amylopectin (waxy) from these plants and any mixtures of the aforementioned starches.
• the granular starch may also be a granular starch modified by any means, physical, chemical and / or enzymatic.
• It may be a fluidized or oxidized granular starch or a white dextrin. It may also be a granular starch modified physico-chemically but having been able to retain the structure of the native starch starting, such as esterified and / or etherified starches, particularly modified by grafting, acetylation, hydroxypropylation, anionization, cationization, crosslinking, phosphatation, succinylation and / or silylation. It may be, finally, a starch modified by a combination of the treatments mentioned above or any mixture of such granular starches.
• this granular starch is chosen from native starches, fluidized starches, oxidized starches, chemically modified starches, white dextrins and any mixtures of these products.
• the granular starch is preferably a wheat or pea granular starch or a granular derivative of wheat or pea starch. It generally has a solubility rate of 20% in deionized water of less than 5% by mass and can be practically insoluble in cold water.
• the starchy material for the preparation of the adhesive composition is a water-soluble starch, which may also come from all botanical origins, including a starch, which is water-soluble, rich in amylose or, conversely, rich in amylopectin (waxy).
• This soluble starch can be introduced as a partial or total replacement of the granular starch.
• the water-soluble starch is used in solid form, preferably substantially anhydrous, i.e. undissolved or non-dispersed in an aqueous or organic solvent. It is therefore important not to confuse, throughout the description that follows, the term "water-soluble” with the term "dissolved”.
• Such water-soluble starches can be obtained by pregelatinization on a drum, by pregelatinization on an extruder, by spraying a suspension or a starch solution, by precipitation with a non-solvent, by hydrothermal cooking, by chemical functionalization or the like. It is in particular a pregelatinized, extruded or atomized starch, a highly converted dextrin (also called yellow dextrin), a maltodextrin, a functionalized starch or a mixture of these products.
• the pregelatinized starches can be obtained by hydrothermal treatment of gelatinization of native starches or modified starches, in particular by steam cooking, jet-cooker cooking, cooking on a drum, cooking in cooking systems. kneader / extruder and then drying, for example in an oven, by hot air on a fluidized bed, on a rotating drum, by atomization, by extrusion or by lyophilization.
• Such starches generally have a solubility in demineralized water at 20% greater than 5% and more generally between 10 and 100% and a starch crystallinity level of less than 15%, generally less than 5% and most often less than 5%. at 1%, or even none.
• PREGEFLO® the products manufactured and marketed by the Applicant under the brand name PREGEFLO®.
• Highly processed dextrins can be prepared from native or modified starches by dextrinification in a weakly acidic acid medium. It may be in particular soluble white dextrins or yellow dextrins. By way of example, mention may be made of the STABILYS® A 053 or TACKIDEX® C 072 products manufactured and marketed by the Applicant. Such dextrins present in demineralized water at 20 °, a solubility generally between 10 and 95% and a starch crystallinity of less than 15% and generally less than 5%.
• Maltodextrins can be obtained by acid, oxidative or enzymatic hydrolysis of starches in an aqueous medium. They may in particular have an equivalent dextrose (DE) of between 0.5 and 40, preferably between 0.5 and 20 and better still between 0.5 and 12.
• DE dextrose
• Such maltodextrins are for example manufactured and marketed by the Applicant under the trade name GLUCIDEX® and have a solubility in demineralized water at 20 ° C, generally greater than 90% or even close to 100% and a crystallinity in lower starch generally less than 5% and usually almost zero.
• the functionalized starches can be obtained from a native or modified starch.
• the high functionalization may for example be carried out by esterification or etherification at a sufficiently high level to confer a solubility in water.
• Such functionalized starches have a soluble fraction as defined above, greater than 5%, preferably greater than 10%, more preferably greater than 50%.
• the functionalization can be obtained in particular by aqueous phase acetylation of acetic anhydride, mixed anhydrides, glutamate hydroxypropylation, dry phase cationization or glue phase, anionization in the dry phase or glue phase by phosphatation or succinylation.
• These water-soluble, highly functionalized starches can have a degree of substitution of between 0.01 and 3, and more preferably between 0.05 and 1.
• the reagents for modifying or functionalizing the starch are of renewable origin.
• the water-soluble starch is a water-soluble starch of wheat or pea or a water-soluble derivative of a wheat or pea starch.
• the starchy material for the preparation of the adhesive composition is an organomodified starch, preferably organosoluble, which may also come from all botanical origins, including an organomodified starch, preferably organosoluble, rich in amylose or, conversely, rich in amylopectin (waxy).
• organosoluble starch may be introduced as partial or total replacement of the granular starch or of the water-soluble starch.
• organomodified starch is intended to mean any polysaccharide material derived from starch, other than a granular starch or a water-soluble starch according to the definitions given above.
• this organomodified starch is almost amorphous, that is to say has a starch crystallinity level of less than 5%, generally less than 1% and especially zero.
• organosoluble that is to say present, at 20 ° C, a fraction soluble in a solvent selected from ethanol, ethyl acetate, propyl acetate, butyl acetate, diethyl carbonate, propylene carbonate, dimethyl glutarate, triethyl citrate, dibasic esters, dimethyl sulfoxide (DMSO), dimethyl isosorbide, glycerol triacetate, isosorbide diacetate, dioleate isosorbide and methyl esters of vegetable oils, at least equal to 5% by weight.
• This soluble fraction is preferably greater than 20% by weight and in particular greater than 50% by weight.
• the organomodified starch may be used according to the invention in solid form, preferably substantially anhydrous.
• the organomodified starch that can be used in the composition according to the invention can be prepared by high functionalization of the native or modified starches such as those presented above.
• This high functionalization can for example be carried out by esterification or etherification at a sufficiently high level to make it essentially amorphous and to confer on it an insolubility in water and preferably a solubility in one of the above organic solvents.
• Such functionalized starches have a soluble fraction as defined above, greater than 5%, preferably greater than 10%, more preferably greater than 50%.
• the high functionalization can be obtained in particular by acetylation in solvent phase by acetic anhydride, grafting for example in the solvent phase or by reactive extrusion, acid anhydrides, mixed anhydrides, fatty acid chlorides, caprolactone oligomers or lactides, hydroxypropylation and crosslinking in the glue phase, cationization and crosslinking in the dry phase or in the glue phase, anionisation by phosphatation or succinylation and crosslinking in the dry phase or in the glue phase, silylation, butadiene telomerization.
• organomodified, preferably organosoluble, highly functionalized starches may in particular be acetates of starches, dextrins or maltodextrins or fatty esters of these starchy materials (starches, dextrins, maltodextrins) with fatty chains of 4 to 22 carbons, all of these products preferably having a degree of substitution (DS) of between 0.5 and 3.0, preferably between 0.8 and 2.8, and especially between 1.0 and 2.7.
• DS degree of substitution
• It may be, for example, hexanoates, octanoates, decanoates, laurates, palmitates, oleates and stearates of starches, dextrins or maltodextrins, in particular having a DS between 0 , 8 and 2.8.
• the organomodified starch is an organomodified starch of wheat or pea or an organomodified derivative of a wheat or pea starch.
• plasticizer of a starchy material any organic molecule, preferably having a molecular weight of less than 5000 g / mol, which, when incorporated in starch by thermomechanical treatment at a temperature between 20 and 200 ⁇ results in a decrease in the glass transition temperature of the starch and / or a reduction in the crystallinity of the starch optionally to a substantially amorphous state, that is to say a crystallinity of less than 15%, preferably less than 5% and more preferably less than 1%.
• Polyols especially sugars such as glucose, maltose, fructose or sucrose are very effective plasticizers of starch.
• the plasticizer useful in the present invention may also be chosen from diols, triols and polyols such as glycerol, polyglycerol, isosorbide, sorbitans, sorbitol, mannitol, and hydrogenated glucose syrups, salts and the like. organic acids such as sodium lactate, urea and mixtures of these products. Water is also a plasticizer of starch.
• the adhesive composition useful to the invention advantageously has, with respect to its total mass, a content of water less than 10% by weight, preferably less than 5%, most preferably less than 1%.
• the molar mass of the plasticizer is preferably less than 1000 g / mol, and in particular less than 400; it may be greater than 18 g / mol.
• the plasticizer of the starch may be chosen from methyl, ethyl or fatty esters of organic acids such as lactic acid, citric acid, succinic acid, adipic acid and glutaric acid and the acetic acid esters.
• fatty esters of monoalcohols, diols, triols or polyols such as ethanol, diethylene glycol, glycerol and sorbitol.
• the plasticizer comprises, relative to the total weight of plasticizer, at least 50% glycerol.
• the rest of the plasticizer may be a polyol or a mixture of polyols chosen from isosorbide, sorbitan, sorbitol, mannitol, and hydrogenated glucose syrups, advantageously sorbitol.
• the adhesive composition useful for the invention also comprises a non-grafted polypropylene and a grafted polypropylene grafted monomer.
• the polypropylene may be a homopolymer, i.e. it is obtained solely from propylene. It can also be a copolymer, that is to say that it is obtained from propylene and from at least one co-monomer capable of copolymerizing with propylene.
• the polypropylene advantageously comprises at least 50%, preferably at least 70%, for example more than 90% by moles of propylene-derived units.
• a comonomer mention may be made of ethylene, isobutene, 4-methyl-pentene or butene-1.
• the copolymer may be a random copolymer or a block copolymer.
• Polypropylene can be isotactic, syndiotactic or atactic, depending on the location of the methyl group on the polymer chain. It is preferably isotactic. It can be semi-crystalline or amorphous. In the case where it is semi-crystalline, it may have a melting temperature in the range of 140 to 190 ⁇ €.
• the MFI of ungrafted polypropylene can range from 0.1 to 500 g / 10 min (ISO 1133-190 ° C-2.16 kg), for example from 0.3 to 100 g / 10 min.
• Polypropylene is generally obtained by catalyzed polymerization.
• Today mainly catalysts (Ziegler-Natta) are used which may consist of phthalate / silicon donors or diether and succinate donors.
• the catalyst may also be of the "metallocene" type, which are single-site catalysts. These are essentially ZrCl 2 catalysts supported on silica and generally used in combination with a cocatalyst such as methylaluminoxane (MAO). These catalysts can be used in combination with Ziegler-Natta catalysts.
• Polypropylene can be made in the gas phase or in suspension.
• Polypropylene grafted with a grafting monomer is obtained by radical reaction of the grafting monomer on the polypropylene.
• one of the polypropylenes mentioned above can be used as polypropylene.
• the mass quantity of grafting monomer reacted on the polypropylene with respect to the weight of the grafted polypropylene is preferably between 0.1% and 10%, in particular between 0.5 and 5%. %.
• the quantity of maleic anhydride can be determined conventionally by assaying the succinic functions by Fourier transform infrared spectroscopy (FTIR).
• FTIR Fourier transform infrared spectroscopy
• the MFI of the grafted polypropylene is advantageously between 0.1 and 500 g / 10 min (ISO 1133-190 ⁇ C-2.16 kg), for example between 20 and 250 g / 10 min, preferably between 80 and 240 g /10 minutes.
• Polypropylenes grafted with maleic anhydride are marketed by Lyondell-Basell ® , Arkema ® or DuPont ® .
• graft a grafting monomer for example maleic anhydride
• the grafting can be accomplished by heating the polymer at elevated temperature, from about 100 ° C to about 300 ° C, in the presence or absence of a solvent, with or without a radical generator.
• the radical generators make it possible to facilitate the radical reaction between the grafting monomer and the polypropylene.
• Peroxides can be used as a generator of radicals.
• the grafting reaction can be carried out according to a batch solution process or a continuous process with a melt mixing tool, for example by extrusion.
• the adhesive composition further comprises a binding agent, in proportions ranging from 0.1 to 15 percent resin. This binding agent may be added to the adhesive composition to allow covalent attachment of at least a portion of the plasticizer, starch, or graft-graft monomer to the polypropylene.
• This binding agent can then be chosen for example from compounds carrying at least two functions, free or masked, identical or different, chosen from isocyanate functions, carbamoylcaprolactams, aldehydes, epoxides, halo, protonic acids, acid anhydrides acyl halides, oxychlorides, trimetaphosphates, alkoxysilanes and combinations thereof.
• H12MDI 4,4'-dicyclohexylmethane diisocyanate
• MDI methylenediphenyl diisocyanate
• TDI toluene diisocyanate
• NDI naphthalene diisocyanate
• HMDI hexamethylene diisocyanate
• LI lysine diisocyanate
• dicarbamoylcaprolactams preferably 1 -1 carbonyl bis caprolactam
• halohydrins that is to say compounds having an epoxide function and a halogen function, preferably epichlorohydrin,
• organic diacids preferably succinic acid, adipic acid, glutaric acid, oxalic acid, malonic acid, maleic acid and the corresponding anhydrides,
• oxychlorides preferably phosphorus oxychloride
• trimetaphosphates preferably sodium trimetaphoshate
• alkoxysilanes preferably tetraethoxysilane
• the composition may further comprise an additional polymer, which may be chosen from the organic polymers mentioned below, and different from the starchy material, the plasticizer, the non-grafted polypropylene, the grafted polypropylene grafted monomer and the any binding agent included in the adhesive composition.
• the additional polymer is advantageously present in amounts of less than 70 phr, preferably less than 20 phr, and even less than 10 phr.
• This additional polymer may in particular be a polyethylene such as high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LDPE).
• the composition may also further comprise additives customary for the manufacture of thermoplastics, capable of improving at least one of the final properties of the composition and / or of facilitating the method of manufacturing said composition.
• the usual additives may be chosen from antioxidants, stabilizers, UV absorbers, antistatic agents, optical brighteners, dyes or pigments, nucleating agents, flame retardants, lubricating agents, antiblocking agents, mold release agents, anti-caking agents, antimicrobials, plasticizers, anti-fungi and blowing agents.
• the composition may also comprise as usual additives reinforcements or fillers, for example natural plant fibers such as sawdust, wood fibers or hemp fibers.
• the composition preferably comprises these additives in amounts of less than 40 phr or even 20 phr.
• the composition may be prepared by melt blending, using conventional techniques for making thermoplastic compositions, using the thermoplastic processing equipment which is temperature controlled, such as mixers or extruders. Depending on the choice of components, the skilled person knows how to choose the conditions of manufacture of the composition in order to homogenize the various constituents. Implementation of the temperature may be 120 to 250 ⁇ €, for example 150 to 210 ° C.
• composition can be prepared in a single step, that is to say that the constituents are introduced simultaneously into the processing equipment, or in several steps, for example in different places of an extruder.
• the binding agent When a binding agent is introduced into the composition during the manufacture of the latter, the binding agent may react at least in part with the plasticizer, the starchy material and / or the maleic anhydride grafted onto the polypropylene. It should be noted that when the binding agent has reacted in part or completely, the composition becomes more viscous.
• the MFI of the composition is preferably between 0.1 and 200 g / 10 min. Those skilled in the art can easily adjust the MFI of the adhesive composition by choosing the various constituents thereof and in particular by choosing constituents a, b, c and d of suitable fluidity and by appropriately adjusting the amount of the adhesive. liaison agent when present.
• the structure according to the invention comprises at least one layer based on metal or organic polymer.
• the term "based on” means that the layer comprises at least 10% by weight of said constituent (metal or organic polymer).
• the organic polymer-based layer comprises at least 50% by weight of organic polymer, preferably at least 70%, in particular at least 90% of organic polymer.
• organic polymer mention may be made of:
• PE ethylene
• PE ethylene
• HDPE high density polyethylene
• LDPE low density polyethylene
• LLDPE linear low density polyethylene
• EVA ethylene-co-vinyl acetate
• EVOH ethylene-co-alkyl acrylate copolymers
• ethylene-co-alkyl methacrylate copolymers ethylene-co-acrylic acid copolymer, ethylene-co-methacrylic acid copolymer, ethylene-co-alcohol copolymer vinylic acid (EVOH);
• PP propylene
• iPP isotactic polypropylene
• APP atactic polypropylene
• PA ⁇ homopolyamides and copolyamides
• PA such as polyamide 6 (PA6), polyamide 6.6 (PA6.6), polyamide 11 (PA1 1), polyamide 12 (PA12);
• styrene such as crystal polystyrene, poly (styrene-co-butadiene), poly (styrene-co-acrylonitrile) (SAN), poly (acrylonitrile-co-butadiene-co-styrene) (ABS), poly (acrylonitrile-co-styrene-co-acrylate) (ASA);
• ⁇ homopolymers or copolymers such as polymethyl acrylate (PMA) or polymethyl methacrylate (PMMA);
• polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly (glycolic acid) (PGA), poly (lactic acid) (PLA), polycaprolactone (PCL), poly (butylene succinate ) (PBS), poly (butylene adipate) (PBA), poly (ethylene succinate) and poly (ethylene adipate);
• ⁇ polyacetals such as polyoxymethylene (POM);
• PC polycarbonates
• thermoplastic starches TPS
• the organic polymer-based layer may also comprise one of the usual additives mentioned above.
• the organic polymer layer is based on a biobased polymer, that is to say polymers obtained from raw materials of plant or animal origin. It may be cellulose, thermoplastic starch, polyamides such as PA1 1, polyesters such as PLA or polyolefins such as polyethylene.
• the polymer-based layer is different from the adhesive composition useful in the invention.
• it is not formed by a composition comprising in bulk:
• the cellulose-based material may be free of polypropylene and thermoplastic starch.
• Cellulose can also be mentioned as an organic polymer that is useful for the invention.
• the cellulose-based materials there may be mentioned all types of wood, modified celluloses, paper or cardboard.
• the cellulose-based material is chosen from modified cellulose or not, paper or cardboard.
• the organic polymer-based layer may be in the form of a film, a woven or a nonwoven.
• the metal-based layer may be metal, a metal alloy or a non-metallic component mixed with a metal, such as silicon doped with at least one metal.
• a metal that can be used in the multilayer structure is iron, zinc, copper, lead or aluminum.
• alloy mention may be made of brass, steel and cast iron.
• the metal is aluminum.
• the presence of the binding agent further enhances adhesion of the adhesive composition to organic polymer or metal-based supports, even when at least a portion of the reactive functions, or even all of the reactive functions. has already reacted at the time of adhering the adhesive composition layer to the organic polymer or metal layer.
• the first layer may be based on an apolar polyolefin and the third layer may be based on metal or polar polymer.
• the mass quantity of adhesive composition may be between 0.5% and 80% of the total mass of the structure, for example between 1% and 60% by weight, the remaining quantity being composed of the other layers based on of organic polymer or metal.
• the layer of the adhesive composition may have a thickness ranging from 1 ⁇ to 3 cm, for example from 10 ⁇ to 1 cm.
• the first and third layers based on metal or organic polymer may have a thickness ranging from 1 ⁇ to 3 cm, for example from 10 ⁇ to 1 cm.
• the total structure can have a thickness ranging from 2 ⁇ to 10 cm.
• a film may have a total thickness ranging from 10 ⁇ to 150 ⁇ .
• Some structures may have the advantage of meeting the requirements for materials intended to be in contact with food. Depending on the use of this structure, they may also have low or high permeability to liquid water, steam, oxygen, nitrogen or gas carbonic.
• a structure comprising the successive LDPE or LDPE / adhesive layer / LDPE or LDPE layers has low permeabilities with liquid water and with water vapor.
• any type of extruded article, laminated or laminated or molded for example by injection.
• the articles of the present invention can be manufactured by conventional techniques for manufacturing multilayer structures employing melt polymers.
• the method of the invention comprises a step of contacting the adhesive composition in the molten or softened state.
• a composition is in the molten or softened state when it has a non-zero melt flow index under conditions of temperature and pressure at the moment of contacting.
• the composition has, for example, an MFI between 0.1 and 200 g / 10 min.
• the temperature of the adhesive composition is from 150 to 250 ° C, preferably 155-210 ⁇ €.
• the method according to the invention may comprise a coextrusion step in the case where the materials of the different layers are brought into contact in the molten state.
• a coextrusion step in the case where the materials of the different layers are brought into contact in the molten state.
• coextrusion blow molding of hollow body co-extrusion inflation also called blowing of sheath (in English "film blowing") and co-extrusion flat ("in English” cast coextrusion ").
• an organic polymer having a suitable MFI may have an MFI ranging from 0.1 to 50 g / 10min.
• a particular object of the invention is a three-layer film obtained by coextrusion of PE structure / adhesive composition / PE, which can be obtained in particular by coextrusion blowing of sheath.
• this film is a three-layer film PEBD / adhesive composition / LDPE.
• the process for manufacturing this film can be carried out in a conventional manner for a person skilled in the art, for example by coextrusion of jacket blasting by coextruding the intermediate adhesive composition at a temperature ranging from 150 to 200 ° C. and the layers of outer polyethylene film at a temperature ranging from 130 ° C to 200 ⁇ €.
• the different thicknesses of this three-layer film can be, relative to the total thickness of the film, from 5 to 40% of the first layer of PE (layer A), from 20 to 90% of the adhesive layer (layer B) and 5 to 40% of the second layer of PE C), the sum of the thicknesses making 100%. Preferentially, these thicknesses range from 10 to 30% for layer A, from 50 to 70% of layer B and from 10 to 30% of layer C.
• Another preferred object of the invention is a hollow body, that is to say a bottle, a bottle or reservoir, bilayer of PE structure / adhesive composition and is obtained by coextrusion, preferably its HDPE structure / adhesive composition.
• the hollow body of the structure has an outer layer consisting of adhesive composition and an inner layer made of PE. This hollow body has a particularly soft feel.
• this hollow body can be carried out in a conventional manner for a person skilled in the art, for example by coextrusion blow molding of hollow bodies by coextruding the adhesive composition at a temperature ranging from 150 to 200.degree. of polyethylene of the hollow body at a temperature ranging from 130 ° C to 200 ° C.
• the hollow body may have a total thickness ranging from 0.4 mm to 4 mm.
• the different thicknesses of this hollow body may be, relative to the total thickness of the film, from 1 to 60% of the adhesive layer (layer D) and from 40 to 99% of the second layer of PE (layer E), the sum of the thicknesses making 100%. Preferably, these thicknesses range from 10 to 50% for layer D and from 50 to 90% of layer E.
• a tube can also be made by coextruding PP, the adhesive composition and PA to form a PA structure tube / adhesive composition / PP.
• the method according to the invention may also comprise a step of applying a layer of polymer in the molten state to a layer based on organic polymer, metal or adhesive composition in the solid state.
• This step may be carried out by pressing, overmolding, lamination or lamination, extrusion-rolling, coating, extrusion-coating or coating.
• the layer of polymer applied in the molten state is the adhesive composition.
• the adhesive composition in the molten state
• the structure can also be manufactured by overmoulding: using this technique, it is possible to manufacture, for example, an HDPE structure / adhesive composition: firstly, a first piece of HDPE is manufactured by injection-molding then, in a second step, applying the adhesive composition by overmolding the cooled HDPE part, overmolding a layer of adhesive composition.
• Applicant having a water content of about 12%;
• Applicant composition containing glycerol and sorbitol having a water content of about 16%;
• Binding agent methylenediphenyl diisocyanate (MDI).
• the adhesive composition (CA) is obtained in the following manner: the various constituents are introduced into a TSA twin-screw extruder having a diameter (D) of 26 mm and a length of 50 D, so as to obtain a flow rate of total material of 15 kg / h.
• the extrusion conditions are as follows:
• thermoplastic composition The constituents of the thermoplastic composition are introduced into the extruder in the following manner:
• the binding agent is introduced in proportions of about 1 phr.
• a water extraction is operated by slight depression at the Z6 zone.
• the composition thus obtained has a density close to 1.1 l and a MFI of 1.1 g / 10 min (190 ° C., 2.16 kg). It has a final water content of about 0.4% (measured by the Karl-Fischer method). It comprises by mass approximately 30% of native starch, 20% of a mixture of glycerol and sorbitol, 25% of polypropylene and 25% of polypropylene grafted with maleic anhydride. Glycerol, sorbitol and starch being extracted from plants, the composition has a content of biosourced constituents of about 50%.
• a three-layer film of PE / CA / PE structure was made from the adhesive composition described above and low density polyethylene Lupolen 2420H (Basell), which corresponds to a film extrusion grade.
• the three-layer PE / CA / PE film is made by coextrusion with a co-extruder with three separate feed extruders. Each die of the extruder feeds a feed-block for melt-contacting the layers of PE and adhesive composition, the molten polymer streams then passing through an annular die, which gap is 0.8 mm.
• the settings of the three extruders are: - Temperature profile: 170 ° C - 175 ° C - 180 ⁇ for the three extruders heating zones and 180 ° C -180 ⁇ C - 180 ° C for zones of die head heating.
• the films thus obtained have a total thickness of 30 microns in thickness.
• the mass ratio of the different layers of the PE / CA / PE film is: 20/60 / 20.
• the materials adhere very well to each other since no delamination was observed between the different layers after the peel test.
• monolayer films acting as controls were prepared. They consist of:
• the water vapor permeabilities of the films are measured according to the ISO 2528 standard by following the following protocol: capsules, containing a desiccant and closed by the material under test, are placed in a temperature and humidity controlled atmosphere. These capsules are weighed at regular time intervals. The increase in the mass makes it possible, as soon as it is proportional to the time interval, to determine the transmission coefficient of the water vapor in g / m 2 / 24h by measuring the coefficient of the straight line gain. mass as a function of time. In general, the permeability to water vapor increases as the thickness of the film decreases. Table 1 below shows for each composition tested the properties of water vapor permeability measured at a temperature of 23 ° C. and 50% RH in moisture.
• a monolayer film of adhesive composition is much more permeable to water vapor than PE film, about five times more (respectively 2.2 against 0.4 g / m 2 / 24h at 80 ⁇ ).
• a monolayer film of MELANGE is less permeable than a monolayer film of the adhesive composition (respectively 2.5 against 3.5 g / m 2 / 24h at 50 ⁇ ).
• the multilayer film according to the invention has a permeability equivalent to the monolayer film of PE (approximately 2.5 g / m 2 / 24h at approximately 30 ⁇ m).
• a monolayer film of 50 ⁇ MELANGE has a permeability equivalent to that multilayer film according to the invention of 30 ⁇ (2.5 g / m 2 / 24h).
• the PE / CA / PE structure according to the invention is therefore very advantageous from an eco-design point of view because it incorporates biobased products and allows a lower material consumption than monolayer films made from a mixture of PE and adhesive composition.
• the Applicant has also carried out work of production of three-layer structures manufactured by hot pressing from different metals and the adhesive layer already described using the following protocol.
• Three granules of the adhesive composition are placed between two identical metal or metal alloy plates (dimensions: 2 cm ⁇ 4 cm). The plates are placed in a temperature-controlled heating press at 180 ° C.
• the metals and metal alloys tested are:
• the structure is made by coextrusion blow molding of HDPE and the adhesive composition.
• HDPE has an MFI of 0.25 measured at 190 ° C and 2.16 kg according to IS01 133.
• the bottles produced have the structure as follows from the outside to the inside:
• the bottles are prepared using a Magic coextrusion line, equipped with two separate extruders whose sheaths are respectively set at a temperature of 170 ° C for the adhesive composition and ⁇ ⁇ ' ⁇ for HDPE .
• the extrusion head including the feedblock and the die, has a stepped temperature between 185 ° C and 160 ° C.
• the outer and inner thickness is chosen by changing the extruder flow rate and thus introducing into the extrusion head more or less HDPE and adhesive composition.
• a first coextrusion blow-molding is thus carried out for which a bottle is obtained whose parison has a thickness of approximately 1 mm, the respective thicknesses both layers being about 10% for the adhesive composition and about 90% HDPE.
• a second coextrusion blow is then performed for which a bottle is obtained, the parison of which has a thickness of approximately 1 mm, the respective thicknesses of the two layers being approximately 50% for the adhesive composition and approximately 50% for the adhesive composition.
• HDPE high density polyethylene
• the two bottles obtained have an excellent appearance and the layers of HDPE and adhesive composition adhere perfectly to each other. They also have a soft feel, this touch being bonded to the outer layer of adhesive composition.

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